Level dyeing of wool polyimine or polyamine and sulfonated phenylene amino-chlorotriazine treated

ABSTRACT

Process for the level dyeing of wool which is provided with an anti-felting finish of polyimine or polyamine resin with fiberreactive dyestuffs, wherein, prior to the dyeing, the wool provided with the anti-felting finish is pretreated with triazine derivatives as described in German Pat. No. 1,290,519 and the dyeing with the reactive dyestuffs is then effected in the usual manner.

United States Patent Cathelin et al.

THE LEVEL DYEING OF WOOL POLYIMINE OR POLYAMINE AND SULFON'ATED PHENYLENE AMlNO-CHLOROTRIAZINE TREATED lnventors: Pierre-Rene'Cathelin, Tignieu,

France; Hermann-Heinz Konrad, Kelkheim, Taunus, Germany Hoechst Aktiengesellschaft, Frankfurt am Main, Germany Filed: Sept. 6, 1973 Appl. No.: 394,797

Assignee:

Foreign Application Priority Data Sept. 8, 1972 Germany 2244060 US. Cl. 8/17; 8/74; 8/18;

8/15 Int. Cl D06p 7/00 Field of Search 8/65, 66, 31, 17, 18

1 June 17, 1975 [56] References Cited UNITED STATES PATEIQTS 2,643,958 6/1953 Klciner et al. 8/17 UX 3,098,697 7/1963 Cappuccio ct al. 8/31 3,278,253 10/1966 Wcckler ct al. A A. 8/17 3,400,121 9/1968 Weckler ct al. 8/17 X 3,743,477 7/1973 Egli was Primary Examiner-Donald Levy Attorney, Agent, or FirmCurtis, Morris & Safford 3 Claims, N0 Drawings 1 THE LEVEL DYElNG OF WOOL POLYIMINE OR POLYAMINE AND SULFONATED PHENYLENE AMINO-CHLOROTRIAZINE TREATED The present invention relates to a process for the level dyeing of polyamide materials.

In practice, wool has normally not been subjected hitherto to a pretreatment in order to be dyed level.

German Pat. No. 1,290,519 describes a process for the streak-free dyeing of polyamide fibers with reactive dyestuffs, wherein auxiliary agents on the basis of triazine derivatives are added to the dyebath to promote uniform absorption of the dyestuffs. In practice, however, other auxiliary levelling agents that have a different action and also a different chemical constitution are also added to the dyebaths. Level dyeing may also be promoted by a more careful selection of the dyestuffs which are suited for this purpose.

On the other hand, it is known that in the dyeing of wool, in particular wool which is provided with an antifelting finish and especially woollen fibers which are provided with a polymine or polyamine finish (according to the method described in Melliand Textilberichte 9/1971, page 1,100, or in the Journal of the Society of Dyers and Colourists, Volume 88, number 3/1972, pages 93 to 100) and which, consequently show an absolutely felting-free behaviour, great difficulties arise with regard to the levelness of the dyeings. These difficulties are due to the fact that within the wool new groups having a dyestuff affinity are activated by the anti-felting finish and have thus a special action in the reactive or salt-like bonding of the dyestuff. The higher this affinity of the wool, the greater the difficulties to obtain level dyeings on this fibrous material. Difficulties are still higher if dyeing is carried out with combinations of two or more dyestuffs, because in most cases the absorption properties of the dyestuffs are very different. On the other hand, one can only use reactive dyestuffs for the dyeing of such anti-felting finished wool, since merely such textile articles are withstanding without felting several washings at 60 C in household washing machines with perborate-containing detergents and must, therefore, also provide a corresponding color-fastness.

These high demands, i.e., several washings at 60 C, are only satisfied by dyeings produced with reactive dyestuffs. But just these generally used reactive dyestuffs distinctly show the affinity differences which are due to the polyamide fibrous material. Thus, for example, if dyeing is carried out with combinations of dyestuffs which, owing to their different content of -SO H- group in the dyestuff molecule (without consideration of any SO l-l group that may be present in the reactive groups), have a different absorption behaviour, the above-described disadvantages become particularly visible. This is also described in the Journal of the Society of Dyers and Colourists, loc. cit., page 96. So the usual antifelting finishes or felting-reducing treatments increase these affinity differences which are due to the material.

Now, we have found that the above-described disadvantages and difficulties which arise in the dyeing with reactive dyestuffs of wool provided with a polyimine or polyamine resin anti-felting finish can be avoided and that completely level dyeings complying with the fastness properties required for the articles prepared from these materials can be obtained with fiber-reactive dyestuffs by pretreating the wool which has been provided with the anti-felting finish, prior to the dyeing operation with compounds of the general formula C l X in which R represents a hydrogen or an alkyl radical, preferably an alkyl radical containing up to 4 carbon atoms, A represents an aliphatic, aromatic, arylaliphatic or cycloaliphatic radical, Z represents an ani- .onic group, preferably chlorine or the group R i A (2),

and Me represents a salt-forming cation, preferably an alkali metal ion, and by effecting the dyeing with the reactive dyestuffs in the usual manner, preferably at elevated temperature according to the exhaust method.

As regards the feasibility of the process of the invention, it is very surprising that the mere pretreatment of the goods with the triazine derivatives of the formula (1) permits the obtention of absolutely uniform and level dyeings (also with combinations of reactive dyestuffs) in the subsequent dyeing with reactive dyestuffs. If the said products of the formula (I) are used simultaneously with the reactive dyestuffs described in German Pat. No. 1,290,519 in the dyebath, no improvements or only slight improvements with regard to the uniformity and levelness of the produced dyeings are obtained.

According to the present invention, the pretreatment of the fibrous material is generally carried out with a goods-to-liquor ratio of 1:25 to 1:5, preferably 1:10 to 1:15, in the following manner:

Prior to dyeing, the wool provided in known manner with an antifelting finish and having the form of combed material, of yarn in hanks, of bobbins or of piece goods, is heated in a liquor acidified with acetic acid to pH 5, starting at 40 C, within 30 minutes to the boiling temperature with one of the mentionedproducts of the formula (I) in a quantity of 0.5% to 5%, referred to the weight of the dry goods, and" 0.01% to. 0.5% of a non-ionic auxiliary agent, for example an oxethylated nonylphenol, treated for 15 minutes at the boiling temperature and then rinsed warm and cold with water. The quantity used of triazine derivative of the formula (I) inversely depends on the intensity of the shade to be dyed later on; thus, for darker dyeings smaller quantities of product are applied. Besides the above-described method it is also possible to pretreat in one united lot several batches of wool which are to' be dyed with almost equal intensity but different shades or, if suitable apparatuses are available, to carry out the dyeing and following dyeing continously.

The application of the pretreatment product from an described in Melliand Textilberichte 9/1971, page 1,100.

The wool yarns were dyed on a hank yarn dyeing machine at a goods-to-liquor ratio of 1:15 with the bath aqueous medium may also be effected by impregnation described hereinafter data referring to the weight of (padding, nip-padding, spraying, etc.) and dwelling or d l) i th following manner: y mp gn and Steamingthe aqueous bath having 40 C and a pH-value of 5 It is also possible to apply the compounds of the fordj d i h acetic id) t i d mllla fmm Organic Solvents Onto the Substrate and 0.1 of a non-ionic auxiliary agent on the basis of to remove the solvents during fixation by steaming or 10 the reaction product f 1 l f l h l d suction. 10 moles of ethylene oxide,

For the following dyeing which is carried out accord and in order to compensate the affinity differences of ing to the usual methods, there maybe used in the prothe 1 cess of the invention the following types of dyestuffs as due to material and fi i h reactive dyestuffs; for example: dyestuffs which contain 1 of the product f the f l a vinyl-sulfone group or which form such a group under the dyeing conditions and which react over this group with the reactive groups of the polyamide fibers, for example dyestuffs which contain sulfatoethylsulfone, C1 chloroethylsulfone, methyltaurinoethyl-sulfone or thiosulfatoethylsulfone groups; C

dyestuffs which react with the fiber of a substituted or unsubstituted acrylamide group, for example dye- I f stuffs which contain a-bromo-acrylamideor B-(2,2,3,- -Q 3-tetrafluoro-cyclobutyl)-acryloylamino groups;

dyestuffs which contain the following atom groupings as reactive groups: monoand di-chlorotriazine, trichloropyrimidine, monochloro-diflu-oropyrimidine, mono-chloroacetic acid amide, chloroor sulfatopropylamide, alkyl-sulfone-propylamide, dichloro- 3O phthalazine, benzochlorothiazole, dichloropyridazone, Aft h i i t d d th ll i l i t th dichloropyrazine and methylsulfonyl-methylbath, this pretreatment bath was heated within minchloropyrimidine. utes to the boiling temperature, the material was then The chromophorous part of these water-soluble dyetreated for 15 minutes under these conditions, rinsed stuffs may be of the most varied structure; according to warm and finally at C with water. the invention, azo dyestuffs and anthraquinone y Dyeing was effected directly after this pretreatment stuffs are used. Such dyestuffs containing the aboveand likewise at a goods-to-liquor ratio of 1:15 and a described reactive systems are known from literature. starting temperature of 40 C, The goods were at first The preparation of the triazine compounds of the fOrtreated for 10 minutes with an aqueous bath which conmula (I) used in the process of the invention is de- 40 mi d scribed in German Pat. No. 1,290,519. 1.11% of the reaction product of 1 mole of stearyl- The following Examples illustrate the invention: amine and 10 moles of ethylene oxide, and

0.39 of dodecyl-sulfonic acid. EXAMPLE 1 Then, the dyestuffs dissolved in hot water were added Undyed yarn in the form of hanks provided with an to this dyebath, i.e., antifelting finish was used as the textile material. The 0.9 of the reactive dyestuff of the formula S0 Na' N=NC-C-CH ll ll 3 HO-C N NaO S N I S0 -CH eCH -N--CH CH SO3H antifelting finish was applied according to the method 3.5 of the reactive dyestuff of the formula 0 H O 3 CH N: SO2-CH2-CH2-NCH2CH2SO3H l 2 5 and 0.5 of the reactive dyestuff of the formula SO Na CH l 3 NH SO -CH -CH --N-CH CHy CH O 3 After having continued dyeing for 10 minutes, the pH- value of the bath was adjusted to 6.5 by means of acetic acid. The bath was then heated within 35 minutes to 75 C and the goods were treated for 30 minutes at this temperature. The dyebath was then heated within 25 minutes to the boiling temperature and the fibrous material was dyed for 60 minutes at the boiling temperature. Within these 60 minutes of boiling, 2.5 of sodium trichloroacetate were added after a boiling period of 40 minutes to the bath in order to improve the fastness. The dyed goods were then rinsed with water in the usual manner at first warm and then cold. A very level brown dyeing was obtained on the wool.

Similar results with regard to the levelness of the dye ings were obtained when effecting the pretreatment with a product of the formula The dyestuffs disclosed above can be obtained by reacting the corresponding dyestuff starting products containing the group SO CH -CH OSO H with N-methyl-aminoethyl-sulfonic acid (=N-methyltaurine) according to the procedure described in US. Pat. No. 3,802,837. The third dyestuff listed above may be prepared according to the procedure disclosed in Example 5 of US. Pat. No. 3,802,837.

EXAMPLE 2 Fully fashioned (confectioned) knit goods of undyed wool, the fibrous material of which had been provided in the form of combed material in a back-washing machine with an anti-felting finish, were pretreated on a paddle dyeing machine at a goods-to-liquor ratio of 1:20 in an aqueous bath in the manner described in Ex ample 1, but using 3 of the product described in said Example, in order to compensate affinity differences of the wool, and then dyed, likewise at a goods-to-liquor ratio of 1:20, in the following manner:

the aqueous dyebath having a temperature of 50 C was combined with 0.74% of the reaction product of 1 mole of stearylamine and moles of ethylene oxide,

0.26% of dodecylsulfonic acid,

10.0% of sodium sulfate (anhydrous),

4.0% of ammonium sulfate and 0.8 of acetic acid (60% strength).

The goods were entered into the bath so prepared and treated for 10 minutes at 50 C; the pH-value of the bath was adusted to 6.5 by means of acetic acid and then the dyestuffs which had been dissolved in hot SO H water were added in the following quantities:

0.05% of the reactive dyestuff of the formula 0.12% of the reactive dyestuff of the formula and 0.3% of the reactive dyestuffs of the formula The dyebath was heated within 15 minutes to 65 C and allowed to stay for 25 minutes at this temperature, then heated within further 20 minutes to the boiling temperature and dyeing of the goods was effected for 30 minutes under these conditions. The bath was cooled to C, adjusted to pH 8 by means of 3 to 4% ammonia (25% strength) and the fibrous material was further treated for 15 minutes at 80 C. The dyeing was subsequently rinsed warm and cold with water. A completely level grey dyeing was obtained.

Without this pretreatment and with an otherwise same dyeing method, an unlevel and unutilizable dyeing was obtained.

EXAMPLE 3 Machine knitting yarns of wool which had been provided with an anti-felting finish were pretreated on a dyeing apparatus at a goods-to-liquor ratio of 1:15 in a manner analogous to that described in Example 1, but using 2% of the product mentioned in said Example, in

order to compensate the affinity differences of the fibrous material and then dyed in the same manner as described in Example 1 but using the following dyestuffs:

1.2% of the reactive dyestuff of the formula The aftertreatment, too, was carried out as described in Example 1. A very level dyeing was obtained on the woolen yarn that had been provided with the antifelting finish.

EXAMPLE 4 Knit goods of undyed wool that had been provided in the form of combed material with an anti-felting finish were pretreated on a jet dyeing machine in the manner described in Example 1 with the product described in said Example in order to compensate affinity differences of the fibrous material and then dyed likewise according to the method described in Example 1 using 3% of the reactive dyestuff of the formula and aftertreated. A level scarlet dyeing was obtained.

We claim:

1. A process for the level dyeing of wool having an anti-felting finish of polyimine or polyamine resin, with fiber-reactive dyestuffs, wherein, prior to the dyeing, the wool having the anti-felting finish is pretreated with a compound of the formula in which R is hydrogen or an alkyl radical having up to four carbon atoms, A is phenylene, Z is an anionic group selected from the group consisting of SO (H,Me) O-SO (H,Me) COO(H,Me) SO -CH -CH -OSO (H,Me),

is an integer from 1 to 3, X is chlorine or the group and Me is an alkali metal ion; and the dyeing with the said reactive dyestuffs is then effected.

2. A process as claimed in claim 1, wherein the pretreatment is effected at a goods-to-liquor ratio of 1:5 to 1:25, with 0.5 to 5% of the product of the formula, referred to the weight of the dry wool, from aqueous solutions according to the exhaust method.

3. A process as claimed in claim 1, wherein the pretreatment product of the formula is applied by padding in a quantity of 0.5 to 5%, referred to the weight of the dry wool, from aqueous solutions and, for fixation, the substrate so treated is then subjected to steaming or mico-ca -cl' dwelling. 

1. A PROCESS FOR THE LEVEL DYEING OF WOOL HAVING AN ANTIFELTING FINISH OF POLYMINE OR POLYAMINE RESIN, WITH FIBERREACTIVE DYESTUFFS, WHEREIN, PRIOR TO THE DYEING, THE WOOL HAVING THE ANTI-FELTING FINISH IS PRETREATED WITH A COMPOUND OF THE FORMULA
 2. A process as claimed in claim 1, wherein the pretreatment is effected at a goods-to-liquor ratio of 1:5 to 1:25, with 0.5 to 5% of the product of the formula, referred to the weight of the dry wool, from aqueous solutions according to the exhaust method.
 3. A process as claimed in claim 1, wherein the pretreatment product of the formula is applied by padding in a quantity of 0.5 to 5%, referred to the weight of the dry wool, from aqueous solutions and, for fixation, the substrate so treated is then subjected to steaming or dwelling. 